EP1054009B1 - Verfahren zur Herstellung von 3-Isochromanonen durch Cyclisierung von o-Chlormehtylphenylessigsäuren - Google Patents
Verfahren zur Herstellung von 3-Isochromanonen durch Cyclisierung von o-Chlormehtylphenylessigsäuren Download PDFInfo
- Publication number
- EP1054009B1 EP1054009B1 EP00108912A EP00108912A EP1054009B1 EP 1054009 B1 EP1054009 B1 EP 1054009B1 EP 00108912 A EP00108912 A EP 00108912A EP 00108912 A EP00108912 A EP 00108912A EP 1054009 B1 EP1054009 B1 EP 1054009B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- chloride
- iodide
- bromide
- radicals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/76—Benzo[c]pyrans
Definitions
- the present invention relates to a new, advantageous method of manufacture of 3-isochromanones by cyclization of o-chloromethyl-phenylacetic acids.
- Isochroman-3-one is in the synthesis of pharmaceuticals and pesticides as an intermediate product of great interest.
- WO 97/12864 describes the use of 3-isochromanone as Intermediate in the manufacture of fungicides and pesticides and from WO 97/48692 the use of 3-isochromanone in the production of certain agricultural products.
- 3-isochromanone is a known compound and a variety of methods for Representation is mentioned in WO 97/48692.
- 3-isochromanone can Baeyer-Villiger oxidation of 2-indanone using hydrogen peroxide in sulfuric acid and acetic anhydride or using m-chloroperbenzoic acid in combination with trifluoroacetic acid or by reacting Bromomethyl-phenylacetic acid with KOH in ethanol with ring closure become.
- WO 97/48692 discloses a synthesis of 3-isochromanone by chlorination of o-methyl-phenylacetic acid with sulfuryl chloride in the presence of radical initiators and by subsequent reaction of the resulting 2-chloromethyl-phenylacetic acid with a base.
- the disadvantage of this method is the formation of one Equivalent salt per equivalent of 3-isochromanone in the reaction of 2-chloromethyl-phenylacetic acid using a base and handling salts containing reaction mixtures.
- 3-isochromanones are obtained by the reaction of an o-chloromethylphenylacetic acid of the formula (II ) with ring closure in the absence of a base.
- the o-chloromethyl-phenylacetic acid is not converted into the corresponding salt of o-chloromethyl-phenylacetic acid by reaction with a base and the corresponding 3-isochromanone is formed from the salt by cyclization, but the hydrogen chloride is presumably formed directly from the o-chloromethyl cleave phenylacetic acid with simultaneous ring closure and formation of the corresponding 3-isochromanone.
- the reaction thus does not proceed via a salt of o-chloromethylphenylacetic acid as an intermediate, which is then cyclized, but instead leads to the corresponding 3-isochromanone with elimination of hydrogen chloride.
- the hydrogen chloride is usually removed thermally in accordance with its formation from the reaction mixture.
- the hydrogen chloride or a mixture containing the hydrogen chloride and the organic solvent can be evaporated off from the reaction mixture, which may contain an organic solvent. If such a mixture is separated off, it is advisable to condense the organic solvent, to separate the hydrogen chloride and, if desired, to return the solvent freed from hydrogen chloride to the reaction.
- the radicals R 1 , R 2 , R 3 and R 4 independently of one another are in particular hydrogen, fluorine, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy, preferably hydrogen, fluorine, C 1 -C 4 -n- Alkyl or C 1 -C 4 -n-alkoxy, or two of the radicals R 1 , R 2 , R 3 and R 4 are linked to one another and form an aliphatic or aromatic ring with 5 to 10 C atoms.
- R 1 , R 2 , R 3 and R 4 are preferably independently of one another hydrogen, fluorine or C 1 -C 4 -alkyl, in particular hydrogen, fluorine or C 1 -C 4 -n-alkyl.
- two, three or four, in particular three or four, of the radicals R 1 , R 2 , R 3 and R 4 are hydrogen.
- the procedure can be carried out in the presence or absence an ionic halide.
- the ionic halide is an alkali, ammonium or Phosphonium halide, especially an alkali or ammonium halide, where Halide means chloride, bromide or iodide, especially iodide or Bromide has.
- the ionic halide is usually used in an amount of 0.005 to 0.5 Equivalents, especially from 0.01 to 0.05 equivalents per equivalent o-Chloromethyl-phenylacetic acid used.
- the reaction takes place at a pressure of 10 Pa to 0.5 MPa, in particular at 100 Pa to 0.2 MPa, preferably at 1000 Pa to 0.12 MPa.
- the reaction is carried out - as already mentioned at the beginning - at a temperature of 100 to 250 ° C, in particular 120 to 220 ° C, preferably 150 to 200 ° C by. print and temperature are chosen so that the resulting during the reaction Hydrogen chloride occurs in gaseous form and in the gaseous state from the Reaction mixture can be separated.
- the process can be carried out in the presence or absence of a organic solvent.
- Particularly suitable organic solvents are dipolar aprotic solvents such as dioxane, tetrahydrofuran, an N- (C 1 -C 18 alkyl) pyrrolidone, ethylene glycol dimethyl ether, a C 1 -C 4 alkyl ester of an aliphatic C 1 -C 6 carboxylic acid, a C.
- dipolar aprotic solvents such as dioxane, tetrahydrofuran, an N- (C 1 -C 18 alkyl) pyrrolidone, ethylene glycol dimethyl ether, a C 1 -C 4 alkyl ester of an aliphatic C 1 -C 6 carboxylic acid, a C.
- the hydrogen chloride formed in the reaction generally escapes in gaseous form from the reaction mixture and can be done in conventional processes Absorption can be recovered and reused. So you get through Absorption of gaseous hydrogen chloride in water an aqueous hydrochloric acid, which can be used in other technical processes when using Organic solvents are able to separate the gaseous hydrogen chloride particularly easy at the boiling point of the organic solvents used. So lets the reaction z. B. in boiling N-methylpyrrolidone at 160 ° C and 0.025 MPa perform particularly well.
- the duration of the reaction depends, among other things, on the reaction temperature and at the use of an organic solvent on the solubility of Hydrogen chloride in the solvent used in the corresponding Reaction temperature.
- the inventive method is suitable for both a continuous and also discontinuous implementation.
- the reaction apparatus consists of a reaction vessel (1 liter glass vessel), equipped with stirrer, a column (25 cm) filled with Raschig rings, one arranged above the column reflux condenser (condenser) and a washing column connected via a line to the reflux condenser, into which gaseous hydrogen chloride is introduced from below, while from above in Countercurrent water is passed through the wash column to hydrogen chloride absorb to form aqueous hydrochloric acid.
- the aqueous hydrochloric acid is on Withdrawn from the bottom of the washing column.
- the head of the wash column is one Vacuum pump connected.
Description
Die Umsetzung verläuft somit nicht über ein Salz der o-Chtormethylphenylessigsäure als Zwischenprodukt, das anschließend cyclisiert wird, sondern führt unter Abspaltung von Chlorwasserstoff zum entsprechenden 3-Isochromanon.
Der Chlorwasserstoff wird üblicherweise entsprechend seiner Bildung aus dem Reaktionsgemisch auf thermischen Wege entfernt. Man kann aus dem Reaktionsgemisch, das ein organisches Lösemittel enthalten kann, den Chlorwasserstoff oder ein den Chlorwasserstoff und das organische Lösemittel enthaltenes Gemisch abdampfen. Trennt man ein derartiges Gemisch ab, so empfiehlt es sich, das organische Lösemittel zu kondensieren, den Chlorwasserstoff abzutrennen und, falls gewünscht, das vom Chlorwasserstoff befreite Lösemittel wieder in die Reaktion zurückzuführen.
Claims (9)
- Verfahren zur Herstellung eines 3-Isochromanons der allgemeinen Formel (I) durch Umsetzung einer o-Chlormethyl-phenylessigsäure der allgemeinen Formel (II) in Abwesenheit einer Base bei einer Temperatur von 100 bis 250 °C in Anwesenheit oder Abwesenheit eines ionischen Halogenids, in Anwesenheit oder Abwesenheit eines organischen Lösemittels und Abtrennung von Chlorwasserstoff, wobei in den Formeln (I) und (II) die Reste R1, R2, R3 und R4 unabhängig voneinander darstellen:ein Wasserstoff- oder Fluoratom;eine NC- oder F3C-Gruppe;einen Alkyl-, Alkoxy- oder Acyloxyrest, mit jeweils 1 bis 18 Kohlenstoffatomen; odereinen C6-C18-Aryloxy-, Aryl- oder Heteroarylrest, wobei als Heteroatome 1 bis 3 Atome aus der Gruppe O, N und/oder S vorhanden sind;oder worin mindestens zwei der Reste R1, R2, R3 und R4 untereinander verknüpft sind und mindestens einen aliphatischen oder aromatischen Ring mit 5 bis 18 C-Atomen bilden.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Reste R1, R2, R3 und R4 unabhängig voneinander Wasserstoff, Fluor, C1-C4-Alkyl oder C1-C4-Alkoxy bedeuten oder zwei der Reste R1, R2, R3 und R4 untereinander verknüpft sind und einen aliphatischen oder aromatischen Ring mit 5 bis 10 C-Atomen bilden.
- Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass zwei, drei oder vier der Reste R1, R2, R3 und R4 Wasserstoff bedeuten.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das ionische Halogenid ein Alkali-, Ammonium- oder Phosphoniumhalogenid ist, wobei Halogenid die Bedeutung Chlorid, Bromid oder lodid hat.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das ionische Halogenid Ammoniumbromid, Lithiumbromid, Natriumbromid, Kaliumbromid, Tetrabutylphosphoniumbromid, Ammoniumchlorid, Dimethylammoniumchlorid, Diethanolammoniumchlorid, Lithiumchlorid, Natriumchlorid, Kaliumchlorid, Tetrabutylphosphoniumchlorid, Ammoniumiodid, Lithiumiodid, Natriumiodid, Kaliumiodid und/oder Tetrabutylphosphoniumiodid ist.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man ein dipolar aprotisches Lösemittel als organisches Lösemittel einsetzt.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das dipolar aprotische Lösemittel Dioxan, Tetrahydrofuran, ein N-(C1-C18-Alkyl)pyrrolidon, Ethylenglykoldimethylether, ein C1-C4-Alkylester einer aliphatischen C1-C6-Carbonsäure, ein C1-C6-Dialkylether, ein N,N-Di-(C1-C4alkyl)amid einer aliphatischen C1-C4-Carbonsäure, Sulfolan, 1,3-Di-(C1-C8-alkyl)-2-imidazolidinon, ein N-(C1-C8-Alkyl)caprolactam, ein N,N,N',N'-Tetra-(C1-C8alkyl)harnstoff, ein 1,3-Di-(C1-C8-alkyl)-3,4,5,6-tetrahydro-2(1H)-pyrimidon, ein N,N,N',N'-Tetra-(C1-C8-alkyl)sulfamid, 4-Formylmorpholin, 1-Formylpiperidin oder 1-Formylpyrrolidin ist.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das dipolar aprotische Lösemittel ein N-(C1-C18-Alkyl)pyrrolidon ist.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das dipolar aprotische Lösemittel N-Methylpyrrolidon, N-Octylpyrrolidon oder N-Dodecylpyrrolidon ist.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19923548 | 1999-05-21 | ||
DE19923548A DE19923548A1 (de) | 1999-05-21 | 1999-05-21 | Verfahren zur Herstellung von 3-Isochromanonen durch Cyclisierung von o-Chlormethylphenylessigsäuren |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1054009A2 EP1054009A2 (de) | 2000-11-22 |
EP1054009A3 EP1054009A3 (de) | 2001-03-14 |
EP1054009B1 true EP1054009B1 (de) | 2002-11-27 |
Family
ID=7908878
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00108912A Expired - Lifetime EP1054009B1 (de) | 1999-05-21 | 2000-04-27 | Verfahren zur Herstellung von 3-Isochromanonen durch Cyclisierung von o-Chlormehtylphenylessigsäuren |
Country Status (6)
Country | Link |
---|---|
US (1) | US6215006B1 (de) |
EP (1) | EP1054009B1 (de) |
JP (1) | JP2001002672A (de) |
AT (1) | ATE228512T1 (de) |
DE (2) | DE19923548A1 (de) |
IL (1) | IL136260A0 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0210370D0 (en) * | 2002-05-07 | 2002-06-12 | Syngenta Ltd | Chemical process |
CN102297924B (zh) * | 2011-06-21 | 2013-10-30 | 上海试四赫维化工有限公司 | 3-异苯并二氢吡喃酮中邻-甲基苯乙酸和2-氯甲基苯乙酸杂质含量的高效液相色谱分析方法 |
CN108774206B (zh) * | 2018-05-25 | 2021-11-19 | 山西大学 | 一种含异苯并二氢吡喃-1-酮骨架的化合物的制备方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9520355D0 (en) | 1995-10-05 | 1995-12-06 | Zeneca Ltd | Chemical process |
GB9612623D0 (en) * | 1996-06-17 | 1996-08-21 | Zeneca Ltd | Chemical process |
DE19815323C2 (de) * | 1998-04-06 | 2000-06-15 | Clariant Gmbh | Verfahren zur Herstellung von Isochroman-3-onen |
-
1999
- 1999-05-21 DE DE19923548A patent/DE19923548A1/de not_active Withdrawn
-
2000
- 2000-04-27 AT AT00108912T patent/ATE228512T1/de not_active IP Right Cessation
- 2000-04-27 EP EP00108912A patent/EP1054009B1/de not_active Expired - Lifetime
- 2000-04-27 DE DE50000808T patent/DE50000808D1/de not_active Expired - Fee Related
- 2000-05-19 US US09/574,332 patent/US6215006B1/en not_active Expired - Fee Related
- 2000-05-21 IL IL13626000A patent/IL136260A0/xx unknown
- 2000-05-22 JP JP2000150165A patent/JP2001002672A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
EP1054009A3 (de) | 2001-03-14 |
DE50000808D1 (de) | 2003-01-09 |
EP1054009A2 (de) | 2000-11-22 |
ATE228512T1 (de) | 2002-12-15 |
DE19923548A1 (de) | 2000-11-23 |
US6215006B1 (en) | 2001-04-10 |
JP2001002672A (ja) | 2001-01-09 |
IL136260A0 (en) | 2001-05-20 |
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